Records 1 - 20 / 397
CD-MUSIC-EDL modeling of Pb2+ adsorption on birnessites : Role of vacant and edge sites
Zhao, Wei ; Tan, Wenfeng ; Wang, Mingxia ; Xiong, Juan ; Liu, Fan ; Weng, Liping ; Koopal, Luuk K. - \ 2018
Environmental Science and Technology 52 (2018)18. - ISSN 0013-936X - p. 10522 - 10531.
adsorption - Birnessite - CD-MUSIC Modeling - Electrical double layer model - External surface - Interlayer space - Manganese oxide - Mn average oxidation state - Pb - Rietveld refinement
The surface complexation modeling of metal adsorption to birnessites is in its infancy compared to the charge-distribution multi-site ion complexation (CD-MUSIC) models for iron/aluminum (hydr)oxides. Therefore, using X-ray diffraction with Rietveld refinement to obtain the reactive sites and their densities, a CD-MUSIC model combined with a Stern-Gouy-Chapman electrical double layer (EDL) model for the external surface and a Donnan model for the interlayer surface is developed for birnessites with different Mn average oxidation state (MnAOS). Proton affinity constants and the charge distributions of Pb surface complexes were calculated a priory. By fitting Pb adsorption data to the model the obtained equilibrium constants (logKPb) of Pb complexes were 6.9-10.9 for the double-corner-sharing and double-edge-sharing Pb2+ complexes on the edge sites and 2.2-6.5 for the triple-corner-sharing Pb2+ complex on the vacancies. The larger logKPb value was obtained for higher MnAOS. Speciation calculations showed that with increasing MnAOS from 3.67 to 3.92 the interlayer surface contribution to the total Pb2+ adsorption increased from 43.2% to 48.6%, and the vacancy contribution increased from 43.9% to 54.7%. The vacancy contribution from interlayer surface was predominant. The present CD-MUSIC-EDL model contributes to understand better the difference in metal adsorption mechanism between birnessite and iron/aluminum (hydr)oxides.
Microfluidic methods to study emulsion formation
Muijlwijk, Kelly - \ 2017
Wageningen University. Promotor(en): C.G.P.H. Schroën, co-promotor(en): C.C. Berton-Carabin. - Wageningen : Wageningen University - ISBN 9789463430715 - 169
emulsions - microfluidics - food emulsions - droplets - adsorption - colloidal properties - emulsies - microfluidics - voedselemulsies - druppels - adsorptie - colloïdale eigenschappen
Emulsions are dispersions of one liquid in another that are commonly used in various products, and methods such as high-pressure homogenisers and colloid mills are used to form emulsions. The size and size distribution of emulsion droplets are important for the final product properties and thus need to be controlled. Rapid coalescence of droplets during emulsification increases droplet size and widens the size distribution, and therefore needs to be prevented.
To increase stability of emulsions, emulsifiers are added to adsorb at the oil-water interface before droplets collide. The time allowed for emulsifier adsorption is typically in the range of sub-milliseconds to seconds and to optimise emulsification processes, emulsifier adsorption and coalescence stability need to be measured in this time-scale, for which the microfluidic methods described in this thesis were developed.
Chapter 2 provides an overview of existing literature on cross-flow microfluidic emulsification. The effects of various parameters such as microfluidic design, shear forces, and interfacial tension forces on droplet formation and the resulting droplet size are discussed, as well as the use of microfluidics to produce food-grade emulsions. Based on this evaluation, the methods to elucidate interfacial tension and coalescence stability are chosen, and these are presented in the next chapters.
To measure emulsifier adsorption in the sub-millisecond time-scale, a tensiometric method was developed using a cross-flow microfluidic Y-junction, which is described in Chapter 3. This method is based on the relation between droplet size and interfacial tension at the moment of droplet formation, which is referred to as the acting interfacial tension. The acting interfacial tension of a system with hexadecane as the dispersed phase and sodium dodecylsulfate (SDS, a model surfactant) solutions as the continuous phase was successfully measured for droplet formation times ranging from 0.4 to 9.4 milliseconds and with high expansion rates (100-2000 s-1). Comparison of these results with data from a drop tensiometer (a conventional, static, and supra-second time-scale method) indicates that mass transport in the microfluidic Y-junction is fast and probably not limited by diffusion.
Emulsifier mass transport conditions were further investigated in Chapter 4. The continuous phase viscosity and velocity were systematically varied and the effect on the acting interfacial tension in presence of water-soluble SDS was measured. We found that the acting interfacial tension was independent of the continuous phase viscosity, but was inversely dependent on continuous phase velocity. Both aspects led us to conclude that convective emulsifier transport in the continuous phase determines the acting interfacial tension in the Y-junction. When using oil-soluble surfactant Span 20 (dissolved in hexadecane), the acting interfacial tension also decreased with increasing continuous phase velocity, and we therefore concluded that convection also dominated mass transport of emulsifiers dissolved in the to-be-dispersed phase.
The Y-junction method was used in Chapter 5 to elucidate the effect of the dispersed phase viscosity on adsorption of the food-grade emulsifiers Tween 20 (dissolved in the continuous water phase) and Span 20 (dissolved in the dispersed oil phase). A reduction in dispersed phase viscosity sped up adsorption of Tween 20, probably because the shorter hydrocarbon made intercalation of the hydrophobic surfactant tail at the interface easier. Dispersed phase viscosity had an even greater effect on adsorption of Span 20 because convective transport towards the interface was increased.
Next to interfacial tension, also coalescence can be measured with microfluidics and a microfluidic collision channel was used in Chapter 6 to measure emulsion coalescence stability shortly after droplet formation under flow. Coalescence of emulsions stabilised with proteins was measured at various concentrations, pH values, and adsorption times. We found that protein concentrations just below the concentration needed for monolayer surface coverage may be used effectively. β-lactoglobulin-stabilised emulsions were most stable. Emulsions stabilised with whey protein isolate (with as main component β-lactoglobulin), were less stable and when these proteins were oxidised, this led to reduced stability, therewith indicating that also the oxidative state of proteins needs to be considered in emulsion formulation.
The relevance of our work for microfluidic research and industrial emulsification processes is discussed in Chapter 7. Microfluidic devices can be used to study emulsion formation and stability under conditions relevant to industrial emulsification processes; at short time-scales and with convective mass transport. In this thesis we used various food-grade ingredients, and with that application in that field has come closer. We expect that the findings on emulsions can also be applied on foams. With the discussed microfluidic devices different aspects that are important for emulsion formation can be decoupled: for example interfacial tension during droplet formation and emulsion coalescence stability. Furthermore, microfluidic methods are available to for example gain insight in emulsion interface mobility and emulsion storage stability, and we envision that all these microfluidic methods will lead to faster ingredient screening, lower ingredient usage, and more energy efficient emulsion production.
Core-shell particles at fluid interfaces : performance as interfacial stabilizers
Buchcic, C. - \ 2016
Wageningen University. Promotor(en): Martien Cohen Stuart, co-promotor(en): R.H. Tromp; Marcel Meinders. - Wageningen : Wageningen University - ISBN 9789462578968 - 140
stabilization - stabilizers - particles - colloidal properties - adsorption - interface - fluids - stabilisatie - stabiliseermiddelen - deeltjes - colloïdale eigenschappen - adsorptie - grensvlak - vloeistoffen (fluids)
There is a growing interest in the use of particles as stabilizers for foams and emulsions. Applying hard particles for stabilization of fluid interface is referred to as Pickering stabilization. By using hard particles instead of surfactants and polymers, fluid interfaces can be effectively stabilized against Ostwald ripening and coalescence. A drawback of the use of hard particles as interfacial stabilizers is that they often experience a pronounced energy barrier for interfacial adsorption and that hard particles are very specific with regard to the type of fluid interface they can adsorb to. Soft particles, on the other hand, are known as good stabilizers against coalescence and they spontaneously adsorb to a variety of different fluid interfaces.
The aim of this thesis was to investigate core-shell particles comprising a hard core and soft shell with regard to their interfacial behaviour and their ability to act as sole stabilizers for foams and emulsions. We hypothesised that the presence of the soft shell allows for easier interfacial adsorption of core-shell particles compared to the hard core particles only. To test this hypothesis, we prepared core-shell particles comprising a solid polystyrene (PS) core and a soft poly-N-isopropylacrylamide (PNIPAM) shell. To ascertain the effect of shell thickness, we prepared a range of core-shell particles with different shell thicknesses, containing identical core particles. We found that core-shell particles are intrinsically surface active and can generate high surface pressures at the air-water interface and oil-water interfaces, whereas core particles seemed to experience a large energy barrier for interfacial adsorption and did not lower the surface tension. We also confirmed by microscopy that core-shell particles are actually adsorbing to the fluid interface and form densely packed interfacial layers. Further, we found that a certain critical thickness of the soft shell is necessary in order to ensure facile interfacial adsorption. If the PNIPAM shell on top of the core particles is well above 100nm thick, particle adsorption at the air-water interface was found to be diffusion limited.
By gentle hand-shaking we were able to produce dispersion of air bubbles and emulsion droplets solely stabilized by core-shell particles. The resulting bubbles still underwent Ostwald ripening, albeit slowly. For oil-in-water emulsions of hexane and toluene, both of which have a relatively high solubility in the continuous phase, we found that core-shell particles can stop Ostwald ripening. The resulting emulsion droplets adopted pronounced non-spherical shapes, indicating a high elasticity of the interface. The high stability and the remarkable non-spherical shape of the emulsion droplets stabilized by core-shell particles were features we also observed for fluid dispersion stabilized by hard particles. This shows that in terms of emulsion stability core-shell particles behave similar to hard particles as interfacial stabilizer.
As to why the differences between the stability of bubble and oil dispersions arise could not be finally answered. Yet, microscopic analysis of the interfacial configuration of core-shell particles at the air-water interface reveals some peculiar insights which may suggest that core-shell particles adsorb in a polymer-like fashion with the soft PNIPAM shells adsorbing to the air-water interface only, while the hard PS cores reside in the continuous phase.
In summary, we showed that core-shell particles with a hard core and a soft shell can indeed combine the advantageous properties of hard and soft particles. The soft shell enables spontaneous adsorption to a variety of fluid interfaces. Despite their spontaneous adsorption, core-shell particles strongly anchor and do not spontaneously desorb from the fluid interface again. Further, the hard core provides enough rigidity to the core-shell particles to allow the establishment of a stress bearing interfacial particle network. This network eventually stops Ostwald ripening in oil-in-water emulsions. Our results therefore show that in the case of oil-water interfaces, core-shell particles can perform better than solely hard particles as interfacial stabilizers.
Assembly of jammed colloidal shells onto micron-sized bubbles by ultrasound
Buchcic, C. ; Tromp, R.H. ; Meinders, M.B.J. ; Cohen Stuart, M.A. - \ 2015
Soft Matter 11 (2015)7. - ISSN 1744-683X - p. 1326 - 1334.
interfacial rheological properties - aqueous foams - stabilized emulsions - contact-angle - particles - water - surfactants - polymerization - nanoparticles - adsorption
Stabilization of gas bubbles in water by applying solid particles is a promising technique to ensure long-term stability of the dispersion against coarsening. However, the production of large quantities of particle stabilized bubbles is challenging. The delivery of particles to the interface must occur rapidly compared to the typical time scale of coarsening during production. Furthermore, the production route must be able to overcome the energy barriers for interfacial adsorption of particles. Here we demonstrate that ultrasound can be applied to agitate a colloidal dispersion and supply sufficient energy to ensure particle adsorption onto the air–water interface. With this technique we are able to produce micron-sized bubbles, solely stabilized by particles. The interface of these bubbles is characterized by a colloidal shell, a monolayer of particles which adopt a hexagonal packing. The particles are anchored to the interface owing to partial wetting and experience lateral compression due to bubble shrinkage. The combination of both effects stops coarsening once the interface is jammed with particles. As a result, stable bubbles are formed. Individual particles can desorb from the interface upon surfactant addition, though. The latter fact confirms that the particle shell is not covalently linked due to thermal sintering, but is solely held together by capillary interaction. In summary, we show that our ultrasound approach allows for the straightforward creation of micron-sized particle stabilized bubbles with high stability towards coarsening.
Comparing foam and interfacial properties of similarly charged protein–surfactant mixtures
Lech, F.J. ; Meinders, M.B.J. ; Wierenga, P.A. ; Gruppen, H. - \ 2015
Colloids and Surfaces. A: Physicochemical and Engineering Aspects 473 (2015). - ISSN 0927-7757 - p. 18 - 23.
sodium dodecyl-sulfate - bovine serum-albumin - air-water interfaces - beta-lactoglobulin - titration calorimetry - binding - sds - adsorption - rheology - layers
The foam stability of protein–surfactant mixtures strongly depends on the charge of the protein and the surfactant, as well as on their mixing ratio. Depending on the conditions, the mixtures will contain free proteins, free surfactants and/or protein–surfactant complexes. To be able to compare different protein–surfactant mixtures, generic knowledge about the occurrence of each of these states and their relative contribution to foam stability is essential. In this work, the foam stability and interfacial properties of bovine serum albumin (BSA) mixed with sodium dodecyl sulphate (SDS) as well the binding of SDS to BSA as are studied at different molar ratios (MR). A comparison is made with ß-lactoglobulin (BLG) mixed with SDS. Both proteins and SDS are negatively charged at pH 7. The foam stability in the presence of small amounts (up to MR 1) of SDS is half the value of the pure protein solutions. The foam stability for both protein surfactant mixtures reaches a minimum at MR 20. A further increase of the MR leads to an increase of foam stability. The foam stability of BLG–SDS at MR >20 follows the foam stability of pure SDS solutions at equivalent concentrations, while BSA–SDS mixtures have an offset and begin to increase from MR >50. This behaviour was also reflected in the surface pressure and complex dilatational elastic moduli, and could be linked to the binding of the surfactant to the proteins. Both proteins bind SDS at high and low affinity binding sites. BSA's high affinity binding sites have a binding stoichiometry of 5.5 molSDS/molprotein, and BLG's high affinity binding site has a stoichiometry of 0.8 molSDS/molprotein (determined by isothermal titration calorimetry). Binding to the low affinity binding sites, occurs with a binding ratio, leading to an accumulation of free surfactants. While the basic mechanisms underlying the foam properties of mixed systems are not explained in detail by this approach, the foam stability plots of both protein surfactant mixtures could be superimposed using the concentration of free SDS.
Transformation by photolysis in water in the pesticide model TOXSWA : implementation report
Beltman, W.H.J. ; Mulder, H.M. ; Horst, M.M.S. ter; Wipfler, E.L. - \ 2015
Wageningen : Alterra (Alterra report 2649) - 47
waterverontreiniging - pesticiden - fotolyse - biochemische omzettingen - waterbodems - adsorptie - ecotoxicologie - modellen - water pollution - pesticides - photolysis - biochemical pathways - water bottoms - adsorption - ecotoxicology - models
The TOXSWA model has been extended with the functionality to simulate photolysis in water. TOXSWA simulates the fate of substances in water bodies to calculate exposure concentrations for aquatic organisms or sediment-dwelling organisms as part of the risk assessment of plant protection products (PPP). Photolysis is modelled as a first-order process, where transformation occurs in the water phase only. The transformation rate is considered to be linearly proportional to global radiation. Studies in outdoor surface water systems can in principle be used to derive the PPP transformation rates due to photolysis.
Phosphorus leaching from soils: process description, risk assessment and mitigation
Schoumans, O.F. - \ 2015
Wageningen : Alterra, Wageningen-UR (Alterra scientific contributions 46) - ISBN 9789462573666 - 261
nutrient leaching - leaching - soil chemistry - adsorption - phosphorus - phosphate leaching - risk assessment - water quality - eutrophication - nutriëntenuitspoeling - uitspoelen - bodemchemie - adsorptie - fosfor - fosfaatuitspoeling - risicoschatting - waterkwaliteit - eutrofiëring
Theory of brushes formed by psi-shaped macromolecules at solid-liquid interfaces
Zhulina, E.B. ; Leermakers, F.A.M. ; Borisov, O.V. - \ 2015
Langmuir 31 (2015)23. - ISSN 0743-7463 - p. 6514 - 6522.
starlike polymer brushes - dendronized polymers - gold nanoparticles - good solvent - surface - polysaccharides - adsorption - dendrimers - coatings
We present a theoretical analysis targeted to describe the structural properties of brushes formed by ¿-shaped macromolecules tethered by terminal segment of stem to planar surface while exposing multiple free branches to the surrounding solution. We use an analytical self-consistent field approach based on the strong stretching approximation, and the assumption of Gaussian elasticity for linear chain fragments of the tethered macromolecules. The effect of weak and strong polydispersity of branches is analyzed. In the case of weakly polydisperse macromolecules, variations in length of branches lead to a more uniform polymer density distribution with slight increase in the brush thickness compared to the case of monodisperse chains with the same degree of polymerization. We demonstrate that in contrast to linear chains, strong polydispersity of ¿-shaped macromolecules does not necessarily lead to strong perturbations in polymer density distribution. In particular, mixed brushes of the so-called “mirror” dendrons (in which number of stem monomers in one component coincides with number of monomers in a branch of the other component, and vice versa) give rise to a unified polymer density distribution with shape independent of the brush composition. The predictions of analytical theory are systematically compared to the results of numerical self-consistent field modeling based on the Scheutjens–Fleer approach
Interactions between nodes in a physical gel network of telechelic polymers; self-consistent field calculations beyond the cell model
Bergsma, J.P. ; Leermakers, F.A.M. ; Gucht, J. van der - \ 2015
Physical Chemistry Chemical Physics 17 (2015)14. - ISSN 1463-9076 - p. 9001 - 9014.
aqueous-solutions - statistical thermodynamics - chain molecules - adsorption - micelles - formulation - copolymers - scattering - neutron - layer
Triblock copolymers, with associative end-groups and a soluble middle block, form flower-like micelles in dilute solutions and a physical gel at higher concentrations. In a gel the middle blocks form bridges between domains/nodes that contain the ends. We combine the self-consistent field theory with a simple molecular model to evaluate the pair potential between the nodes. In this model the end-groups are forced to remain in nodes and the soluble middle blocks are in solution. When the distance between the centres of the nodes is approximately the corona diameter, loops can transform into bridges, and the pair potential is attractive. Due to steric hindrance, the interaction is repulsive at smaller distances. Till now a cell-model has been used wherein a central node interacts through reflecting boundary conditions with its images in a spherical geometry. This artificial approach to estimate pair potentials is here complemented by more realistic three-gradient SCF models. We consider the pair interactions for (i) two isolated nodes, (ii) nodes positioned on a line (iii) a central node surrounded by its neighbours in simple cubic ordering, and (iv) a central node in a face centred cubic configuration of its neighbours. Qualitatively, the cell model is in line with the more refined models, but quantitative differences are significant. We also notice qualitative differences for the pair potentials in the specified geometries, which we interpret as a breakdown of the pairwise additivity of the pair potential. This implies that for course grained Monte Carlo or molecular dynamics simulations the best choice for the pair potentials depends on the expected node density.
Leaching of plant protection products and their transformation products : proposals for improving the assessment of leaching to groundwater in the Netherlands : version 2
Boesten, J.J.T.I. ; Linden, A.M.A. van der; Beltman, W.H.J. ; Pol, J.W. - \ 2015
Wageningen : Alterra, Wageningen-UR (Alterra report 2630) - 105
bodemchemie - adsorptie - pesticiden - uitspoelen - chemische afbraak - schatting - modellen - soil chemistry - adsorption - pesticides - leaching - chemical degradation - estimation - models
Assessment of leaching of plant protection products to groundwater is an important aspect of the environmental risk assessment of these substances. Analysis of available Dutch groundwater monitoring data for these substances triggered a critical review of the current Dutch leaching assessment. As a result, proposals were developed for improving this assessment. These include: (i) a procedure for correcting systematic errors in measured sorption coefficients, (ii) a preliminary procedure for a quality check of Freundlich exponents, (iii) a flow chart for obtaining parameters describing the relationship between the organic-matter/water distribution coefficient, Kom, and the pH for weak acids, (iv) a procedure for obtaining a Kom endpoint from a population of Kom values including lower and upper limits, (v) a procedure for estimating the total amount of substance in soil from a concentration profile (needed for assessment of degradation half-lives from field experiments). This report is an update of the proposals reported in 2011 by the same authors based on testing the feasibility of the proposals to a few dossiers
A process synthesis approach for isolation of isoflavones from okara
Jankowiak, L. ; Mendez Sevillano, D. ; Boom, R.M. ; Ottens, M. ; Zondervan, E. ; Goot, A.J. van der - \ 2015
Industrial & Engineering Chemistry Research 54 (2015)2. - ISSN 0888-5885 - p. 691 - 699.
driven process synthesis - antioxidant activity - food - adsorption - extraction - separation - products - recovery - integration - components
Owing to the complexity of food matrices, process synthesis methodologies have not been as widely applied in the food industry as in the chemical industry. Here, we describe the application of a process synthesis methodology to design a system to separate valuable components from a byproduct of the soymilk production. The method yielded a number of potential processing pathways and relevant mechanistic questions, which required experimental input. The combination of considering the overall system on the level of general transformations, heuristics, and additional insights through experiments resulted in a simplified conceptual process design for the separation of isoflavones from okara with a globally more sustainable choice. The holistic approach within process design as an implication of the methodology is discussed.
Phosphorus leaching from soils: process description, risk assessment and mitigation
Schoumans, O.F. - \ 2015
Wageningen University. Promotor(en): Sjoerd van der Zee, co-promotor(en): Wim Chardon. - Wageningen : Wageningen University - ISBN 9789462572997 - 261
nutriëntenuitspoeling - uitspoelen - bodemchemie - adsorptie - fosfor - fosfaatuitspoeling - risicoschatting - waterkwaliteit - eutrofiëring - nutrient leaching - leaching - soil chemistry - adsorption - phosphorus - phosphate leaching - risk assessment - water quality - eutrophication
Er zijn succesvolle management strategieën voor P nodig om de waterkwaliteit te verbeteren en daarvoor is allereerst kwantitatieve informatieve nodig over de ruimtelijke verdeling van de fosfaatbelasting van het oppervlaktewater vanuit landbouwgronden. In Nederland is een protocol fosfaatverzadigde gronden ontwikkeld om het potentiële risico van verhoogde fosfaatconcentraties in het bovenste grondwater (op termijn) te voorspellen voor kalkarme zandgronden, omdat in deze gebieden veel intensieve veehouderij voorkomt. Voor deze grondsoort zijn de parameters voor het protocol vastgesteld. Echter, voor de overige grondsoorten is geen informatie verzameld, waardoor er voor Nederland als geheel geen ruimtelijke beeld bestaat van de mate van fosfaatverzadiging en van het potentiële risico van verhoogde fosfaatconcentraties in het bovenste grondwater. Daarnaast is er behoefte aan eenvoudige methoden om het (huidige) actuele risico van de fosfaatbelasting van het oppervlaktewater in kaart te brengen, zodat inzichtelijk gemaakt kan worden welke gebieden nu al substantieel de oppervlaktewaterkwaliteit en de eutrofiestatus beïnvloeden.
On the edge energy of lipid membranes and the thermodynamic stability of pores
Pera, H. ; Kleijn, J.M. ; Leermakers, F.A.M. - \ 2015
Journal of Chemical Physics 142 (2015). - ISSN 0021-9606 - 14 p.
molecular-dynamics simulations - interacting chain molecules - statistical thermodynamics - bilayer-membranes - phase-transition - cell-membranes - adsorption - model - size - vesicles
To perform its barrier function, the lipid bilayer membrane requires a robust resistance against pore formation. Using a self-consistent field (SCF) theory and a molecularly detailed model for membranes composed of charged or zwitterionic lipids, it is possible to predict structural, mechanical, and thermodynamical parameters for relevant lipid bilayer membranes. We argue that the edge energy in membranes is a function of the spontaneous lipid monolayer curvature, the mean bending modulus, and the membrane thickness. An analytical Helfrich-like model suggests that most bilayers should have a positive edge energy. This means that there is a natural resistance against pore formation. Edge energies evaluated explicitly in a two-gradient SCF model are consistent with this. Remarkably, the edge energy can become negative for phosphatidylglycerol (e.g., dioleoylphosphoglycerol) bilayers at a sufficiently low ionic strength. Such bilayers become unstable against the formation of pores or the formation of lipid disks. In the weakly curved limit, we study the curvature dependence of the edge energy and evaluate the preferred edge curvature and the edge bending modulus. The latter is always positive, and the former increases with increasing ionic strength. These results point to a small window of ionic strengths for which stable pores can form as too low ionic strengths give rise to lipid disks. Higher order curvature terms are necessary to accurately predict relevant pore sizes in bilayers. The electric double layer overlap across a small pore widens the window of ionic strengths for which pores are stable.
Partitioning of humic acids between aqueous solution and hydrogel. 3. Microelectrodic dynamic speciation analysis of free and bound humic metal complexes in the gel phase
Yasadi, K. ; Pinheiro, J.P. ; Zielinska, K. ; Town, R.M. ; Leeuwen, H.P. van - \ 2015
Langmuir 31 (2015)5. - ISSN 0743-7463 - p. 1737 - 1745.
dissolved organic-matter - stability-constants - alginate gel - thin-films - adsorption - ions - fluorescence - substances - cells - soil
The hydrogel/water partitioning of the various species in the cadmium(II)/soil humic acid (HA) system is studied for two types of gel, using in situ microelectrodic voltammetry. Under the conditions of this work, with HA particles of ca. 25 and 125 nm radius, the CdHA complex is shown to be close to nonlabile toward a 12.5 µm radius microelectrode. This implies that its kinetic contribution to Cd2+ reduction at the medium/microelectrode interface is practically negligible. The polyacrylamide (PAAm) gels equilibrate with the aqueous medium under significant sorption of HA at the gel backbone/gel medium interface, which in turn leads to induced sorption of Cd(II) in the form of immobilized gel-bound CdHA. The rather high total Cd content of the PAAm gel suggests that the binding of Cd2+ by the hydrophobically gel-bound HA is stronger than that for dispersed HA particles. Still, the intraparticulate speciation of Cd(II) over Cd2+ and CdHA corresponds to an intrinsic stability constant similar to that for simple monocarboxylate ligands such as acetate. Alginate gels are negatively charged, and their free [Cdaq2+] is higher than that in the medium by the corresponding Donnan coefficient. On top of that, Cd2+ is specifically sorbed by the gel backbone/gel medium interface to reach accumulation factors as high as a few tens. HA and CdHA accumulate in the outer 20 µm film of gel at the gel/water interface of both gels, but they do not penetrate into the bulk of the alginate gel. Overall, the gel/water interface dictates drastic changes in the speciation of Cd/HA as compared to the aqueous medium, with distinct features for each individual type of gel. The results have broad significance, for example, for predictions of reactivity and bioavailability of metal species which inherently involve partitioning and diffusion into diverse gel layers such as biointerfacial cell walls, biofilm matrices, and mucous membranes.
|Afvangen van fosfaat uit bloembollensector met ijzerzand : Test van maatregelen die fosforemissie verminderen
Chardon, W.J. ; Groenenberg, J.E. ; Jansen, S. ; Buijert, A. ; Talens, R. ; Krol, A.F. - \ 2014
Bodem 24 (2014)6. - ISSN 0925-1650 - p. 20 - 22.
vollegrondsteelt - bloembollen - bodemchemie - emissiereductie - fosfaten - adsorptie - ijzer - bollenstreek - outdoor cropping - ornamental bulbs - soil chemistry - emission reduction - phosphates - adsorption - iron - bollenstreek
In het oppervlaktewater van de Bollenstreek is de fosfaatconcentratie veel hoger dan de norm van de Europese Kaderrichtlijn Water. Met ijzerzand, een nevenproduct van drinkwaterproductie, kan fosfaat worden afgevangen. Het hoogheemraadschap van Rijnland heeft drie maatregelen op basis van ijzerzand laten onderzoeken op hun effectiviteit. Welke was de beste?
One-step synthesis of delta-MnO2 nanoparticles using ascorbic acid and their scavenging properties to Pb(II), Zn(II) and methylene blue
Wang, M.X. ; Pang, P. ; Koopal, L.K. ; Qiu, G.H. ; Wang, Y. ; Liu, F. - \ 2014
Materials Chemistry and Physics 148 (2014)3. - ISSN 0254-0584 - p. 1149 - 1156.
high-temperature decomposition - manganese oxide - structural evolution - oxidation-state - layered mno2 - birnessite - adsorption - mechanism - nanobelts - dissolution
To obtain delta-MnO2 particles with a large specific surface area, MnO2 was synthesized in an ice-water bath using ascorbic acid (AA) to reduce KMnO4. At pH 3 and 5 and KMnO4/AA molar ratios of 8/1 and 10/1, nanoparticles of delta-MnO2 were produced. The specific surface areas (SSAs) of the samples ranged from 163 to 207 m(2)/g. The Mn average oxidation state of the samples ranged from 3.88 to 3.98 and increased with the KMnO4/AA ratio and pH. The adsorption of the samples with respect to metal ion revealed pseudo adsorption capacities of 3425 mmol Pb2+/kg and 1789 mmol Zn2+/kg. The decolorization behaviors of sample S10-5 (produced at pH 5 and KMnO4/AA molar ratios of 10/1) to methylene blue (MB) were compared at different pH values and temperatures. After 120 min at room temperature, 97% of the MB was adsorbed, and approximately 68% was oxidized. The adsorbed amount and the level of oxidation increased with increasing temperature and decreased with increasing pH. (C) 2014 Elsevier B.V. All rights reserved.
Direct observation of ionic structure at solid-liquid interfaces: A deep look into the Stern layer
Siretanu, I. ; Ebeling, D. ; Andersson, M.P. ; Stipp, S.L.S. ; Philipse, A. ; Cohen Stuart, M.A. ; Ende, D. van den; Mugele, F. - \ 2014
Scientific Reports 4 (2014). - ISSN 2045-2322 - 7 p.
molecular-dynamics - charging behavior - atomic-resolution - surface-charge - gibbsite - adsorption - water - (hydr)oxides - force - kaolinite
The distribution of ions and charge at solid-water interfaces plays an essential role in a wide range of processes in biology, geology and technology. While theoretical models of the solid-electrolyte interface date back to the early 20th century, a detailed picture of the structure of the electric double layer has remained elusive, largely because of experimental techniques have not allowed direct observation of the behaviour of ions, i.e. with subnanometer resolution. We have made use of recent advances in high-resolution Atomic Force Microscopy to reveal, with atomic level precision, the ordered adsorption of the mono- and divalent ions that are common in natural environments to heterogeneous gibbsite/silica surfaces in contact with aqueous electrolytes. Complemented by density functional theory, our experiments produce a detailed picture of the formation of surface phases by templated adsorption of cations, anions and water, stabilized by hydrogen bonding.
Mesoscale models of dispersions stabilized by surfactants and colloids
Sman, R.G.M. van der; Meinders, M.B.J. - \ 2014
Advances in Colloid and Interface Science 211 (2014). - ISSN 0001-8686 - p. 63 - 76.
dissipative particle dynamics - fluid-fluid interfaces - lattice-boltzmann simulations - phase-separation dynamics - pickering emulsions - soluble surfactants - amphiphilic fluids - binary fluids - adsorption - flows
In this paper we discuss and give an outlook on numerical models describing dispersions, stabilized by surfactants and colloidal particles. Examples of these dispersions are foams and emulsions. In particular, we focus on the potential of the diffuse interface models based on a free energy approach, which describe dispersions with the surface-active agent soluble in one of the bulk phases. The free energy approach renders thermodynamic consistent models with realistic sorption isotherms and adsorption kinetics. The free energy approach is attractive because of its ability to describe highly complex dispersions, such as emulsions stabilized by ionic surfactants, or surfactant mixtures and dispersions with surfactant micelles. We have classified existing numerical methods into classes, using either a Eulerian or a Lagrangian representation for fluid and for the surfactant/colloid. A Eulerian representation gives a more coarse-grained, mean field description of the surface-active agent, while a Lagrangian representation can deal with steric effects and larger complexity concerning geometry and (amphiphilic) wetting properties of colloids and surfactants. However, the similarity between the description of wetting properties of both Eulerian and Lagrangian models allows for the development of hybrid Eulerian/Lagrangian models having advantages of both representations.
Influence of the relative humidity on the morphology of inkjet printed spots of IgG on a non-porous substrate.
Mujawar, L.H. ; Kuerten, J.G.M. ; Siregar, D.P. ; Amerongen, A. van; Norde, W. - \ 2014
RSC Advances : An international journal to further the chemical sciences 4 (2014)37. - ISSN 2046-2069 - p. 19380 - 19388.
experimental-verification - protein microarrays - dna microarrays - contact-angle - evaporation - surfaces - drops - performance - fabrication - adsorption
During the drying of inkjet printed droplets, the solute particles (IgG-Alexa-635 molecules) in the drop may distribute unevenly on the substrate, resulting in a “coffee-stain” spot morphology. In our study, we investigated the influence of the relative humidity on the distribution of inkjet printed fluorophore labeled IgG molecules on a polystyrene substrate. A theoretical model for an evaporating droplet was developed in order to predict the changes in the spot diameter, height and volume of a drying droplet. An experiment was performed where a sessile droplet was monitored using a CCD camera installed on a goniometer and good agreement was found between the experimental results and simulation data. We also compared the predicted morphology for an inkjet-printed microarray spot with the experimental results where IgG molecules were printed for various relative humidities. The spot morphology of the dried spots was analyzed by a confocal laser microscopy. At a lower relative humidity (i.e.,
Catalytic Deoxygenation of Fatty Acids: Elucidation of the Inhibition Process
Hollak, S.A.W. ; Jong, K.P. de; Es, D.S. van - \ 2014
ChemCatChem 6 (2014)9. - ISSN 1867-3880 - p. 2648 - 2655.
stearic-acid - mesoporous carbon - vegetable-oils - diesel fuel - continuous decarboxylation - palladium catalysts - reaction pathways - supported nickel - hydrocarbons - adsorption
Catalytic deoxygenation of unsaturated fatty acids in the absence of H2 is known to suffer from significant catalyst inhibition. Thus far, no conclusive results have been reported on the cause of deactivation. Here we show that CC double bonds present in the feed or the products dramatically reduce the deoxygenation activity of supported palladium catalysts. In the case of stearic acid deoxygenation the addition of 0.1 equivalents of a mono-unsaturated fatty acid or olefin already reduces the catalytic deoxygenation activity by 60¿%. This effect becomes more pronounced with an increasing number of double bonds. The inhibition is shown to be reversible in H2 atmosphere, indicating no significant contribution from irreversibly deposited hard coke. Furthermore, the type of support material has no apparent effect on catalyst inhibition. Hence we propose that initial catalyst inhibition proceeds through reversible adsorption of CC double bonds on the palladium active sites.